Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
  • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
• • G—PHYSICS
  • G06—COMPUTING; CALCULATING OR COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
• • G—PHYSICS
  • G06—COMPUTING; CALCULATING OR COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
  • G06F3/047—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means using sets of wires, e.g. crossed wires
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
  • G09G5/00—Control arrangements or circuits for visual indicators common to cathode-ray tube indicators and other visual indicators
  • G09G5/003—Details of a display terminal, the details relating to the control arrangement of the display terminal and to the interfaces thereto
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
  • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
  • H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
• • G—PHYSICS
  • G06—COMPUTING; CALCULATING OR COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
  • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
  • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
  • G09G2300/00—Aspects of the constitution of display devices
  • G09G2300/04—Structural and physical details of display devices
  • G09G2300/0404—Matrix technologies
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
  • H05K2203/1131—Sintering, i.e. fusing of metal particles to achieve or improve electrical conductivity

Definitions

• the present invention relates to a method for manufacturing a conductive pattern.
• a method for forming a conductive pattern on a circuit board that is, a method for producing a conductive pattern
• a paste in which conductive particles are dispersed in a resin is applied, dried, exposed and developed to form a fine pattern, and then heated.
• a method is known in which conductive patterns are made to contract by contracting a pattern formed by the above process so that the conductive particles are brought into contact with each other (see Patent Documents 1 to 3).
• the conventional method for producing a conductive pattern requires that heat treatment for bringing conductive particles into contact with each other to develop conductivity is performed at a high temperature for a long time, and the production efficiency when this is applied to actual production. was significantly lower. Moreover, since there is a high possibility that a heat treatment for a long time at a high temperature deteriorates a member such as a substrate, there is a demand for a manufacturing method for obtaining a fine conductive pattern while avoiding these problems. Met.
• An object of the present invention is to provide a method for producing a conductive pattern.
• the present invention has the following configurations (1) to (11).
• a conductive pattern manufacturing method comprising an exposure step of exposing a film or pattern on a substrate containing conductive particles A and an organic compound B with light having a broad spectrum to obtain a conductive film or a conductive pattern.
• the process for producing a conductive pattern according to (1) comprising: a developing step of developing the film to obtain a conductive pattern.
• the light having a broad spectrum is light selected from the group consisting of light from a xenon lamp, light from a xenon flash lamp, and light from a halogen lamp, according to any one of (1) to (4) above.
• a method for producing a conductive pattern is (6) The method for producing a conductive pattern according to any one of (1) to (5), wherein the exposure step shields light having a wavelength of less than 400 nm.
• a touch sensor comprising a conductive pattern manufactured by the method for manufacturing a conductive pattern according to any one of (1) to (16).
• a touch panel comprising the touch sensor according to (17).
• a display panel comprising the touch sensor according to (18).
• a conductive pattern having good conductivity can be obtained without high-temperature and long-time heat treatment, and production efficiency can be remarkably improved. Is possible.
• the method for producing a conductive pattern according to the first aspect of the present invention comprises an exposure step of obtaining a conductive film by exposing a film containing conductive particles A and an organic compound B with light having a broad spectrum.
• the manufacturing method of the conductive pattern of the 2nd aspect of this invention is equipped with the exposure process of exposing the pattern containing the electroconductive particle A and the organic compound B with the light which has a broad spectrum, and obtaining a conductive pattern. It is characterized by.
• Examples of the conductive particles A include particles of Ag, Au, Cu, Pt, Pb, Sn, Ni, Al, W, Mo, ruthenium oxide, Cr, Ti, indium, or alloys of these metals.
• Ag, Cu or Au particles are preferable, and Ag particles are more preferable from the viewpoint of low cost and stability.
• the volume average particle diameter of the conductive particles A is preferably 0.01 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m, and even more preferably 1 to 5 ⁇ m. If the volume average particle diameter is 0.05 ⁇ m or more, the contact probability between the conductive particles A is improved, and the specific resistance value and the disconnection probability of the obtained conductive pattern are lowered. Further, since the light for exposure is smoothly transmitted through the dry film, it is easy to form a fine pattern. Further, when the volume average particle diameter is 1 ⁇ m or more, a more uniform dispersion state is easily obtained, and the specific resistance value is further reduced.
• the volume average particle diameter of the conductive particles A can be measured by a dynamic light scattering method using a light scattering particle size distribution analyzer (for example, manufactured by HORIBA).
• the amount of the conductive particles A added is preferably 70 to 95% by mass, more preferably 80 to 90% by mass, based on the total solid content in the conductive paste, which is a raw material for the film or pattern subjected to the exposure process. If it is 70 mass% or more, the contact probability between the conductive particles A in curing shrinkage is particularly improved, and the specific resistance value and the disconnection probability of the obtained conductive pattern are lowered. If it is 95% by mass or less, light for exposure is smoothly transmitted through the dry film, so that a fine pattern can be easily formed.
• the total solid content in the conductive paste refers to all components of the conductive paste excluding the organic solvent.
• the organic compound B is preferably a compound having an unsaturated double bond, a glycidyl group or a carboxyl group.
• a photosensitive organic compound is preferable.
• the monomer, oligomer, or polymer which has a polymerizable unsaturated group is mentioned, for example.
• polymerizable unsaturated group examples include ethylenically unsaturated groups such as vinyl group, allyl group, acrylate group, and methacrylate group, or acrylamide group.
• Examples of monomers having a polymerizable unsaturated group include allylated cyclohexyl diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, and methoxylation.
• the addition amount of the monomer having a polymerizable unsaturated group is preferably 1 to 15% by mass, more preferably 2 to 10% by mass with respect to the total solid content in the conductive paste. If it is less than 1% by mass, the sensitivity is lowered and it is difficult to form a fine pattern. If it exceeds 15 mass%, the exposure mask will come into contact with the resulting tack and become contaminated, causing problems such as performance deterioration.
• an ethylenically unsaturated group into an oligomer or polymer for example, an ethylenically unsaturated compound having a glycidyl group or an isocyanate group with respect to a mercapto group, amino group, hydroxyl group or carboxyl group of the oligomer or polymer, or Examples thereof include a method of adding 0.05 to 1 molar equivalent of acrylic acid chloride, methacrylic acid chloride or allyl chloride.
• Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, crotonic acid glycidyl ether, and isocrotonic acid glycidyl ether.
• Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate or (meth) acryloylethyl isocyanate.
• the organic compound B contains a non-photosensitive monomer, oligomer or polymer having no unsaturated double bond in order to bring the conductive particles A into contact with each other and to improve the adhesion to the substrate.
• these non-photosensitive monomers having no unsaturated double bond preferably have a cyclic structure in order to absorb light more efficiently.
• the non-photosensitive polymer having no unsaturated double bond include an epoxy resin, a novolac resin, a phenol resin, a polyurethane, a silicon resin, a melamine resin, a polyimide precursor, or a closed ring polyimide.
• epoxy resin examples include ethylene glycol-modified epoxy resin, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, and novolac type epoxy resin. , Alicyclic epoxy resin, glycidylamine type epoxy resin, glycidyl ether type epoxy resin or heterocyclic epoxy resin.
• the conductive paste preferably contains a photopolymerization initiator C.
• the photopolymerization initiator C include a radical photopolymerization initiator and a cationic photopolymerization initiator, and may be appropriately selected depending on the light used in the exposure step.
• radical photopolymerization initiator examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 1-phenyl-1,2-propanedione-2- ( o-ethoxycarbonyl) oxime, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzyl-butanone, benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin Propyl ether, benzoin isobutyl ether, benzophenone, methyl
• complexes of cationic dyes and borate anions that absorb in the near ultraviolet combinations of silver halides sensitized with near infrared sensitizing dyes and reducing agents, titanocene, iron arene complexes, organic peroxides And radical generators such as hexaaryl, biimidazole, N-phenylglycine or diaryliodonium salts, or sensitizing dyes such as 3-substituted coumarins, cyanine dyes, merocyanine dyes, thiazole dyes or pyrylium dyes.
• Examples of the cationic photopolymerization initiator include iodonium salts, sulfonium salts, phosphate salts, and antimonate salts.
• the addition amount of the photopolymerization initiator C is preferably 0.05 to 10% by mass and more preferably 0.1 to 10% by mass with respect to the conductive paste from the viewpoint of photocurability and compatibility.
• the sensitivity can be improved by using a sensitizer together with the photopolymerization initiator, and the effective wavelength range for the reaction can be expanded.
• the sensitizer examples include 2,3-bis (4-diethylaminobenzal) cyclopentanone, 4,4-bis (dimethylamino) chalcone, p-dimethylaminocinnamylidene indanone, 2- (p -Dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone 3,3-carbonylbis (7-diethylaminocoumarin), triethanolamine, methyldiethanolamine, triisopropanolamine, N- Phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, methyl 4-dimethylaminobenzoate or 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole, etc. It is done.
• the addition amount of the sensitizer is preferably 0.05 to 10% by mass, more preferably 0.1 to 10% by mass with respect to the organic compound B from the viewpoint of photocurability and compatibility.
• the conductive paste contains a non-photosensitive polymer having no unsaturated double bond
• the conductive paste includes a compound having a carboxyl group, a compound having a hydroxyl group such as a polyhydric alcohol, It is preferable that modified amine, polyfunctional phenol, imidazole, mercaptan, isocyanate, melamine, acid anhydride or the like is included.
• Examples of the compound containing a carboxyl group include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and structural formula Compounds corresponding to (1) include 2-methylmalonic acid, 2-ethylmalonic acid, 2-propylmalonic acid, 2-butylmalonic acid, 2- (3-methoxypropyl) malonic acid, 2- (3-propoxy Propyl) malonic acid, 2- (3-propoxybutyl) malonic acid, (E) -2- (hex-4-ethyl) malonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2-propylsuccinic acid, 2-butylsuccinic acid, 2- (3-methoxypropyl) succinic acid, 2- (3-propoxypropyl) succinic acid, 2- (3-prop
• a compound obtained by dehydration condensation of the above two molecules of carboxylic acid may be used.
• the polyhydric alcohol include 1,2-decanediol, 1,10-decanediol, 1,2-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, Examples include 1,2-tetradecanediol, 1,16-hexadecanediol, 1,2-hexadecanediol, alkylene dihydric alcohols such as polyethylene glycol and polypropylene glycol, trimethyloloctane, dipentaerythritol, and tripentaerythritol cellulose.
• the conductive paste preferably contains an organic solvent from the viewpoint of adjusting the viscosity and improving the surface smoothness of the coating film.
• the conductive paste viscosity (value measured at 3 rpm with a Brookfield viscometer) is preferably 10 to 100 Pa ⁇ s from the viewpoint of coating failure due to sedimentation of the conductive particles A, prevention of dripping or improvement of the coating property. s is more preferable.
• organic solvent examples include methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, ⁇ -butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, and chlorobenzoic acid.
• Examples of the conductive paste include leveling agents such as organic or inorganic pigments, glass powders, fillers, plasticizers, special vinyl polymers or special acrylic polymers, surfactants, silane coupling agents, and antifoaming agents. Additives such as an agent or an antioxidant may be blended.
• organic pigments include carbon materials such as activated carbon, acetylene black, ketjen black, carbon black, titanium black, carbon whisker, or carbon nanotube, dyes, pigments, ultraviolet absorbers, visible light absorbers, or infrared absorbers. Is mentioned.
• Examples of the ultraviolet absorber, visible light absorber or infrared absorber include azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, anthraquinone dyes, benzophenone dyes, triazine dyes, p-aminobenzoic acid.
• Examples thereof include cyano dye compounds, salicylic acid compounds, and indole compounds, and azo dyes, benzophenone compounds, cyanoacrylate compounds, and indole compounds are preferable.
• these compounds include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4 ′.
• -Dimethoxybenzophenone 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone Hydrate, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 -Hydroxy-4- (2-G Roxy-3-methacryloxy) propoxybenzophenone, 2-ethylhexyl-2-cyano-3,3-dipheny
• inorganic pigments examples include Ru, Cr, Fe, Co, Mn, Cu, Ni, and oxides of these metals. By blending these inorganic pigments which are black powders, light absorption and scattering in the exposure process can be controlled.
• the glass powder or filler preferably has a volume average particle diameter of 0.05 to 5 ⁇ m from the viewpoint of controlling light scattering in the exposure step, Bi 2 O 3 , SiO 2 , B 2 O 3 , ZrO 2 , More preferably, Al 2 O 3 , TiO 2 or ZnO, or rare earth metals such as alkali metals, alkaline earth metals or cerium, or oxides of these metals are blended.
• plasticizer examples include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, and glycerin.
• silane coupling agent examples include methyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and vinyltrimethoxysilane. Methoxysilane is mentioned.
• the conductive paste can be prepared by mixing necessary materials and then kneading with, for example, a three-roller.
• the film or pattern subjected to the exposure process of the present invention can be obtained by a coating process.
• the coating step is a step of applying a conductive paste on a substrate to obtain a coating film or a coating pattern.
• a film such as a PET film, a polyimide film, a polyester film or an aramid film, an epoxy resin substrate, a polyetherimide resin substrate, a polyether ketone resin substrate, a polysulfone resin substrate, an alkali glass substrate
• a glass plate of a non-alkali glass substrate or a glass / epoxy resin composite substrate a silicon wafer, an alumina substrate, an aluminum nitride substrate, or a silicon carbide substrate, and a film or a glass plate is preferable.
• the surface of these substrates may be covered with one or more of a transparent conductive film or pattern, a decorative film, or an insulating film.
• the transparent conductive film or pattern for example, ITO composed of tin-doped indium oxide, FTO composed of fluorine-doped tin oxide, copper, zinc oxide, titanium oxide, nano silver wire, carbon nanotube, graphene, conductive polymer
• ITO tin-doped indium oxide
• FTO fluorine-doped tin oxide
• membrane or pattern of these is mentioned.
• tempered glass subjected to tempering treatment is preferable.
• the tempered glass for example, chemically tempered glass in which molecules on the glass surface layer are ion-exchanged to form large molecules on the glass surface and compressive stress is formed on the glass surface layer, or a temperature at which residual stress remains in the glass.
• Physically tempered glass in which compressive stress is formed on the glass surface layer by rapid cooling after heating up to is mentioned.
• the substrate on which the conductive pattern is formed may be a continuous long substrate.
• the conductive pattern can be manufactured using, for example, a reel-to-reel method or a roll-to-roll method.
• a method such as a roll-to-roll method is used, a plurality of lines can be obtained at a time if the substrate is arranged in parallel on the front and back surfaces with the irradiation light at the center, which is efficient.
• Examples of methods for obtaining a coating film or coating pattern by applying a conductive paste on a substrate include spin coating using a spinner, spray coating, roll coating, screen printing, offset printing, gravure printing, letterpress printing, flexographic printing. Alternatively, a method using a blade coater, a die coater, a calendar coater, a meniscus coater or a bar coater may be mentioned.
• the thickness of the obtained coating film or coating pattern is generally adjusted so that the thickness of the dried film or drying pattern obtained by drying the coating film or coating pattern is in the range of 1 to 20 ⁇ m.
• the film or pattern obtained by the coating process may be subjected to a drying process as necessary.
• the drying step is a step of drying the coating film or coating pattern obtained in the coating step to obtain a dry film or drying pattern.
• the organic solvent and the like are removed from the coating film by drying in the drying step.
• drying method in the drying step examples include heat treatment using an oven or a hot plate, irradiation with light such as infrared rays, drying under reduced pressure, or a combination thereof.
• the heat treatment temperature is preferably 50 to 180 ° C.
• the heat treatment time is preferably 1 minute to several hours.
• the coating film obtained by the coating process may be subjected to a pre-exposure process as necessary.
• the pre-exposure step is a step in which the coating film obtained in the coating step is exposed with light having bright lines to obtain an exposure film in which the pattern shape is recorded on the conductive film.
• Examples of the light having a bright line include a mercury lamp having a line spectrum in the ultraviolet region or a xenon lamp having a line spectrum in the near infrared region.
• the bright line is preferably i-line (365 nm), h-line (405 nm) or g-line (436 nm), and more preferably matches the absorption spectrum of the organic compound or photopolymerization initiator C.
• the exposure film obtained by the pre-exposure process may be subjected to a pre-development process as necessary.
• the pre-development step is a step of developing the exposure film obtained in the pre-exposure step to obtain a pattern.
• the pre-development step is a step of developing the exposure film obtained in the pre-exposure step to obtain a pattern.
• the development include alkali development using an alkaline developer or organic development using an organic solvent, with alkali development being preferred.
• Examples of the development include alkali development using an alkaline developer or organic development using an organic solvent, with alkali development being preferred.
• alkaline developer examples include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethyl
• examples include an aqueous solution of aminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine.
• aqueous solutions include, for example, polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or ⁇ -butyrolactone, methanol, ethanol or isopropanol.
• polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or ⁇ -butyrolactone, methanol, ethanol or isopropanol.
• Alcohols, esters such as ethyl lactate or propylene glycol monomethyl ether acetate
• ketones such as cyclopentanone, cyclohexanone, isobutyl ketone or methyl isobutyl ketone, or a surfactant may be added.
• Development can be performed by a method such as showering the exposed film with a developing solution while the substrate is allowed to stand or rotate, or immersing the substrate together with the exposed film in the developing solution.
• the pattern obtained may be rinsed with a rinse solution.
• a rinse solution examples include water and alcohols such as ethanol or isopropyl alcohol or esters such as ethyl lactate or propylene glycol monomethyl ether acetate added to water.
• the exposure step in the present invention is a step of exposing a film or pattern obtained through a coating step, a pre-exposure step, a pre-development step or a drying step to obtain a conductive film or a conductive pattern.
• the organic compound B contained in the film or pattern contains a photosensitive organic compound
• the photosensitive organic compound photoreacts and the film or pattern shrinks due to the exposure in the exposure process and the presence of the photopolymerization initiator C.
• the conductive particles A come into contact with each other to develop conductivity.
• heat treatment may be performed before or after exposure or simultaneously with exposure.
• Examples of the heat treatment method include heating using an oven, an inert oven or a hot plate, or irradiation with infrared rays.
• the pattern shape can be recorded on the film by shielding the exposure light in a desired pattern shape through the exposure mask.
• the exposure process may be performed while cooling the substrate.
• the exposure light in the exposure step needs to be light having a broad spectrum in order to obtain suitable conductivity, but it is preferable that both the minimum wavelength and the maximum wavelength are in the range of 200 to 3000 nm. More preferably, either the minimum wavelength or the maximum wavelength is in the range of 400 to 1500 nm.
• An extra wavelength region of light having a broad spectrum may be shielded by an optical filter or a prism.
• the substrate absorbs light of less than 400 nm well, it is preferable to shield light of less than 400 nm in order to prevent deterioration of the substrate, the decorative film on the substrate surface, the insulating film, or the ITO thin film.
• Examples of light sources having a broad spectrum include xenon lamps, halogen lamps, deuterium lamps, LEDs, lasers, plasmas, light-emitting diodes, incandescent bulbs, or light sources using cantal wires, tungsten, or carbon for filaments.
• a xenon lamp or a halogen lamp capable of emitting light including a near infrared region is preferable, and a xenon lamp is more preferable.
• the xenon lamp refers to a lamp that utilizes light emission by discharge in a rare gas such as xenon, neon, argon, helium or krypton.
• pulse irradiation refers to a light irradiation method in which continuous irradiation and intermittent irradiation are repeated instantaneously, that is, a method of periodically irradiating light.
• the repetition conditions of continuous irradiation and intermittent irradiation, the period of light irradiation in pulse irradiation, that is, pulse irradiation conditions can be controlled by the frequency, which is the number of pulse repetitions per second.
• the amount of energy of the irradiated light can be controlled by the pulse width and the number of pulses.
• pulse irradiation is preferable in that it can instantaneously irradiate strong light or weak light, so that rapid modification of the conductive pattern and the substrate is prevented.
• the pulse irradiation time and frequency may be appropriately selected depending on the composition of the conductive pattern and the type of the substrate. Pulse irradiation is an effective means for the purpose of improving production efficiency, preventing excessive light scattering, preventing deterioration of the base material, and the like. More specifically, the pulse irradiation time is preferably 0.03 msec to 100 msec when the exposure is performed using a xenon flash lamp. When the total pulse irradiation time exceeds 100 msec, the film base material may be distorted. If it is less than 0.05 msec, the resulting conductive film or conductive pattern has insufficient conductivity.
• pulse irradiation with a total pulse irradiation time of 1 to 60 seconds.
• a total pulse irradiation time of 5 minutes or less is preferable.
• the irradiation time is excessively long, the base material is significantly deteriorated.
• light having a bright line may be irradiated.
• a mercury xenon lamp may be used, or light from a xenon lamp and a mercury lamp may be simultaneously irradiated.
• the pre-exposure process and the exposure process can be performed simultaneously.
• the exposure light in the exposure process may be irradiated from either the front surface or the back surface of the substrate.
• the irradiation light can be controlled more precisely, and improvement in production efficiency and improvement in adhesion between the substrate and the conductive pattern can be expected.
• the front and back exposure light may be the same or different.
• drying in said drying process is performed by light irradiation
• the drying process and the exposure process can be performed collectively.
• the developing step in the first aspect of the present invention is a step of developing the conductive film obtained in the exposure step to obtain a conductive pattern.
• a desired pattern has already been formed in the coating process, or in the pre-exposure process and the pre-development process, and the conductive pattern is formed when the exposure process is completed. Since it is obtained, the development step is unnecessary.
• the conductive pattern shape recorded on the conductive film is exposed, and a desired conductive pattern is formed.
• alkali development is preferable as in the pre-development step.
• the development can be performed by a method such as showering the conductive film with a developer while leaving or rotating the substrate, or immersing the substrate together with the conductive film in the developer, as in the pre-development step.
• the obtained conductive pattern may be subjected to a rinsing treatment with a rinsing liquid in the same manner as in the pre-development step.
• a second exposure step of exposing the conductive pattern with light having a broad spectrum may be performed. More specifically, for example, exposure is performed with light having a bright line, development is performed, a fine conductive pattern is formed, and then exposure is further performed with light having a broad spectrum in the second exposure step. A highly conductive conductive pattern can be obtained.
• the conductive pattern manufactured by the manufacturing method of the present invention and the transparent conductive film or pattern on the substrate surface are preferably in contact for conduction.
• the transparent conductive film or pattern on the substrate surface may further be in contact with a member such as a decorative film, an insulating film, or a light shielding film.
• the decorative film refers to a resin film formed by mixing a white or black pigment, a curing agent, and an additive.
• the surface of the decorative film may be covered with a metal thin film such as Mo, Ni, Al, or Nd.
• the insulating film may be formed at a site where the conductive pattern needs to be insulated.
• the insulating film refers to, for example, an acrylic resin or a siloxane resin, or a resin film formed by mixing these resins with fine powder such as silica or titania.
• the touch panel manufactured using the conductive pattern obtained by the manufacturing method of the present invention includes a decorative film formed on the substrate, an insulating film covering all or part of the light shielding film, a protective film, a transparent conductive film, etc. Consists of.
• the conductive pattern is in contact with all or part of the light shielding film, the insulating film, the protective film, or the transparent conductive film, and particularly functions as a lead wiring of the touch panel.
• Conductive particles (A-1) Ag powder produced by a wet reduction method (volume average particle size 1.19 ⁇ m, specific surface area 1.12 m 2 / g, tap density 4.8 g / cm 3 )
• Conductive particles (A-2) Ag powder produced by a wet reduction method (volume average particle size 0.4 ⁇ m, specific surface area 2.50 m 2 / g, tap density 3.1 g / cm 3 )
• Conductive particles (A-4) Ag powder produced by a wet reduction method (volume average particle size 6.1 ⁇ m, specific surface area 0.17 m 2 / g, tap density 4.2 g / cm 3 )
• Organic compound (B-1) 60 g of binder polymer (TR-2500; manufactured by Negami Kogyo Co., Ltd.
• Organic compound (B-2): Acid value 85, photosensitive acrylic polymer having a weight average molecular weight of 32,000 (APX-716; manufactured by Toray Industries, Inc.)
• GMA glycidyl methacrylate
• Resin solution X was obtained. 120 g of photosensitive resin solution X and 380 g of conductive particles (A-1) were mixed and kneaded with three rollers (EXAKT M-50; manufactured by EXAKT) to obtain conductive paste X.
• a conductive paste Q was obtained by mixing 140.5 g of conductive particles (A-3) with the photosensitive resin solution Z obtained by the same method as above and kneading the mixture with three rollers.
• Example 1 A conductive paste X was applied on a glass substrate by screen printing to obtain a coating film.
• the obtained coating film was heat-treated in a 100 ° C. ventilation oven for 1 hour and dried to obtain a dried film.
• the resulting dried film is exposed by irradiating light from an exposure machine (LA3000F; manufactured by Dainippon Screen Mfg. Co., Ltd.) equipped with a xenon flash lamp through an exposure mask (applied voltage 3200 V; irradiation time 0.6 msec).
• LA3000F manufactured by Dainippon Screen Mfg. Co., Ltd.
• a xenon flash lamp through an exposure mask (applied voltage 3200 V; irradiation time 0.6 msec).
• the obtained conductive film was developed by showering with an aqueous solution of 0.3% by mass sodium carbonate at 30 ° C. for 30 seconds, and then rinsed with water to remove non-exposed portions to obtain a stripe-shaped conductive pattern. It was.
• the line resistance was measured using a resistivity meter (Loresta (registered trademark) GP; manufactured by Mitsubishi Chemical Corporation) with a line width of 50 ⁇ m and a line length of 45 mm, it was 105 ⁇ .
• the distortion and color change of the substrate did not occur and it was good.
• Example 2 On the glass substrate, the conductive paste X was applied in a stripe pattern by screen printing to obtain a stripe-shaped coating pattern.
• the obtained stripe-shaped coating pattern was heat-treated in a 100 ° C. ventilation oven for 1 hour and dried to obtain a stripe-shaped dry pattern.
• the resulting stripe-shaped dry pattern was exposed by irradiating light from an exposure machine equipped with a xenon flash lamp (applied voltage 3200 V; irradiation time 0.8 msec) to obtain a stripe-shaped conductive pattern. .
• Example 3 On the glass substrate, the conductive paste Y was applied by screen printing to obtain a coating film.
• the obtained coating film was heat-treated in a 100 ° C. ventilation oven for 1 hour and dried to obtain a dried film.
• the obtained dried film is exposed by irradiating light of an exposure machine (PEM-6M; manufactured by Union Optics Co., Ltd.) equipped with a mercury lamp through an exposure mask at an exposure amount of 200 mJ / cm 2 (wavelength 365 nm conversion). As a result, an exposed film was obtained.
• PEM-6M manufactured by Union Optics Co., Ltd.
• the obtained exposed film was developed in the same manner as the conductive film of Example 1, and then rinsed with water to remove non-exposed portions, thereby obtaining a stripe-shaped conductive pattern.
• the obtained conductive pattern was further exposed by irradiating light from an exposure machine (LA3000F; manufactured by Dainippon Screen Mfg. Co., Ltd.) equipped with a xenon flash lamp.
• LA3000F manufactured by Dainippon Screen Mfg. Co., Ltd.
• the line resistance when the line width was 50 ⁇ m and the line length was 45 mm was 90 ⁇ . Moreover, the distortion and color change of the substrate did not occur and it was good.
• Example 4 A striped conductive pattern was obtained in the same manner as in Example 3 except that the conductive paste Z was used instead of the conductive paste Y.
• Example 5 A striped conductive pattern was obtained in the same manner as in Example 3 except that the conductive paste P was used in place of the conductive paste Y.
• the line resistance when the line width was 50 ⁇ m and the line length was 45 mm was 130 ⁇ . Moreover, the distortion and color change of the substrate did not occur and it was good.
• Example 6 A striped conductive pattern was obtained in the same manner as in Example 3 except that the conductive paste Q was used in place of the conductive paste Y.
• the line resistance when the line width was 50 ⁇ m and the line length was 45 mm was 80 ⁇ . Moreover, the distortion and color change of the substrate did not occur and it was good.
• Example 7 A striped conductive pattern was obtained in the same manner as in Example 3 except that the conductive paste R was used in place of the conductive paste Y.
• the line resistance at a line width of 50 ⁇ m and a line length of 45 mm was 170 ⁇ . Moreover, the distortion and color change of the substrate did not occur and it was good.
• Example 8 A conductive pattern was obtained in the same manner as in Example 3 except that a PET film substrate was used instead of the glass substrate, and a light wavelength 400 nm cut filter was used as the light source.
• the line resistance when the line width was 50 ⁇ m and the line length was 45 mm was 70 ⁇ . Moreover, the distortion and color change of the substrate did not occur and it was good.
• Example 9 An exposed film was obtained in the same manner as in Example 3 except that a PET film substrate was used instead of the glass substrate. The obtained exposed film was developed in the same manner as the conductive film of Example 1, and then rinsed with water to remove non-exposed portions, thereby obtaining a stripe-shaped conductive pattern.
• the obtained conductive pattern was further exposed by irradiating light from an exposure machine (manufactured by Heraeus Co., Ltd.) equipped with a xenon flash lamp (applied voltage 400 V; irradiation time 0.2 msec).
• the line resistance when the line width was 50 ⁇ m and the line length was 45 mm was 130 ⁇ . Moreover, the distortion and color change of the substrate did not occur and it was good.
• Example 10 The same operation as in Example 3 was performed to obtain an exposed film.
• the obtained exposed film was developed in the same manner as the conductive film of Example 1, and then rinsed with water to remove non-exposed portions, thereby obtaining a stripe-shaped conductive pattern.
• the obtained conductive pattern was further exposed (energy density 20 kW / m 2 ; irradiation time 5 minutes) by irradiating light of a short wavelength infrared ray generator (maximum energy wavelength 1.2 ⁇ m; manufactured by Heraeus Co., Ltd.).
• the line resistance when the line width was 50 ⁇ m and the line length was 45 mm was 80 ⁇ . Moreover, the distortion and color change of the substrate did not occur and it was good.
• Example 11 The same operation as in Example 3 was performed to obtain an exposed film.
• the obtained exposed film was developed in the same manner as the conductive film of Example 1, and then rinsed with water to remove non-exposed portions, thereby obtaining a stripe-shaped conductive pattern.
• the obtained conductive pattern was further exposed by irradiation with light from a short- and medium-wavelength infrared generator (carbon type; maximum energy wavelength 2.0 ⁇ m; manufactured by Heraeus Co., Ltd.) (energy density 20 kW / m 2 ; irradiation time 3 minutes) did.
• a short- and medium-wavelength infrared generator carbon type; maximum energy wavelength 2.0 ⁇ m; manufactured by Heraeus Co., Ltd.
• the line resistance when the line width was 50 ⁇ m and the line length was 45 mm was 80 ⁇ . Moreover, the distortion and color change of the substrate did not occur and it was good.
• Example 12 The same operation as in Example 3 was performed to obtain an exposed film.
• the obtained exposed film was developed in the same manner as the conductive film of Example 1, and then rinsed with water to remove non-exposed portions, thereby obtaining a stripe-shaped conductive pattern.
• the obtained conductive pattern was further exposed (energy density 25 kW / m 2 ; irradiation time 2 minutes) by irradiation with light from a medium wavelength infrared ray generator (maximum energy wavelength 2.6 ⁇ m; manufactured by Heraeus Co., Ltd.).
• the line resistance when the line width was 50 ⁇ m and the line length was 45 mm was 80 ⁇ . Moreover, the distortion and color change of the substrate did not occur and it was good.
• Example 13 An exposed film was obtained in the same manner as in Example 3 except that a PET film substrate was used instead of the glass substrate. The obtained exposed film was developed in the same manner as the conductive film of Example 1, and then rinsed with water to remove non-exposed portions, thereby obtaining a stripe-shaped conductive pattern.
• the obtained conductive pattern was further exposed by irradiating light from a medium wavelength infrared ray generator (energy density 25 kW / m 2 ; irradiation time 1 minute).
• the obtained stripe-shaped coating pattern was heat-treated in a 100 ° C. ventilation oven for 1 hour and dried to obtain a stripe-shaped dry pattern.
• the obtained stripe-shaped dried pattern was heat-treated in a ventilated oven at 140 ° C. for 10 minutes to obtain a stripe-shaped conductive pattern.
• Comparative Example 2 Except that the heat treatment time for the striped dry pattern was changed to 30 minutes, the same operation as in Comparative Example 1 was performed to obtain a striped conductive pattern.
• the line resistance with a line width of 50 ⁇ m and a line length of 45 mm was 200 ⁇ , and the resistance value was high, which was not practical.
• Comparative Example 3 A striped conductive pattern was obtained in the same manner as in Comparative Example 1 except that a PET film substrate was used instead of the glass substrate and the heat treatment time of the striped dry pattern was changed to 1 hour.
• the present invention is useful as a method for producing a conductive pattern on a circuit board or the like of a touch panel.

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